US11802244B1 - Gemini surfactant for use in recycling lithium batteries - Google Patents
Gemini surfactant for use in recycling lithium batteries Download PDFInfo
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- US11802244B1 US11802244B1 US18/186,584 US202318186584A US11802244B1 US 11802244 B1 US11802244 B1 US 11802244B1 US 202318186584 A US202318186584 A US 202318186584A US 11802244 B1 US11802244 B1 US 11802244B1
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 238000002386 leaching Methods 0.000 claims 1
- 239000011236 particulate material Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229920005596 polymer binder Polymers 0.000 abstract description 9
- 239000002491 polymer binding agent Substances 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003945 anionic surfactant Substances 0.000 abstract description 3
- 229940125904 compound 1 Drugs 0.000 abstract description 3
- 238000000527 sonication Methods 0.000 abstract description 3
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical class [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/20—Phosphonium and sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the disclosure of the present patent application relates to surfactants, and particularly to a gemini surfactant for use in recycling lithium batteries.
- lithium batteries may provide an alternative to fossil fuels for powering electric automobiles.
- Lithium batteries are made from various materials, including lithium, cobalt, aluminum, copper, manganese, nickel, and graphite. Since the metal layers tend to become delaminated, an organic polymer, most frequently polyvinylidene fluoride (PVDF) is used to bind the materials together, as well as to facilitate the exchanges of electric charges between the electrodes.
- PVDF polyvinylidene fluoride
- mechanical processes are used to separate the copper and aluminum foils used at the electrodes from the remaining fine particles (often referred to in the art as a “black mass”), which undergo pyrolysis or hydrometallurgical processes to remove the binder, which adheres to the fine particles.
- HF hydrogen fluoride
- fluorocarbons requiring expensive scrubbers to remove harmful admissions, or use harsh solvents under extreme conditions.
- gemini surfactants which include two long hydrophobic tails, each tail headed by a small hydrophilic head, the heads being joined by a short bridge.
- gemini surfactants which include two long hydrophobic tails, each tail headed by a small hydrophilic head, the heads being joined by a short bridge.
- gemini surfactant for use in recycling lithium batteries solving the aforementioned problems is desired.
- the gemini surfactant for use in recycling lithium batteries is an anionic surfactant having the generic formula C x H 2x+1 (C y H 2y+1 ) PO 4 C z H 2z PO 4 C x H 2x+1 (C y H 2y+1 ).
- Current solvents used to remove polymer binders include Nmethyl-2-pyrrolidone (NMP), N—N-dimethylformamide (DMF), N—N-dimethylacetamide (DMAC), N—N-dimethylsulfoxide (DMSA), and ethanol.
- the benchmark solvent often used to dissolve polymer binders is NMP.
- the present surfactants are phosphate-based surfactants and are used with a phosphate-based solvent, namely, triethyl phosphate (TEP), which is cheaper and more environmentally friendly than NMP.
- TEP triethyl phosphate
- the present surfactants are used with sonication to remove polymer binders.
- the surfactant(s) are made by reacting alkyl biphosphonate with the corresponding alcohol. The reaction occurs in tetrahydrofuran (THF) at room temperature.
- the surfactants are dissolved in triethyl phosphate (TEP) at a concentration of 1% wt.
- TEP triethyl phosphate
- “Black mass” material from disassembled lithium batteries) is mixed with the solution at 10% wt.
- the sample is sonicated at a high frequency (between 20 to 80 kHz) to remove the PVDF binder.
- the metal oxide powder is leached and separated by solvent extraction.
- the gemini surfactant for use in recycling lithium batteries is an anionic surfactant having the generic formula C x H 2x+1 (C y H 2y+1 ) PO 4 C z H 2z PO 4 C x H 2x+1 (C y H 2y+1 ).
- Current solvents used to remove polymer binders include Nmethyl-2-pyrrolidone (NMP), N—N-dimethylformamide (DMF), N—N-dimethylacetamide (DMAC), N—N-dimethylsulfoxide (DMSA), and ethanol.
- the benchmark solvent often used to dissolve polymer binders is NMP.
- the present surfactants are phosphate-based surfactants and are used with a phosphate-based solvent, namely, triethyl phosphate (TEP), which is cheaper and more environmentally friendly than NMP.
- TEP triethyl phosphate
- the present surfactants are used with sonication to remove polymer binders.
- the surfactant(s) are made by reacting alkyl biphosphonate with the corresponding alcohol. The reaction occurs in tetrahydrofuran (THF) at room temperature.
- the surfactants are dissolved in triethyl phosphate (TEP) at a concentration of 1% wt.
- TEP triethyl phosphate
- “Black mass” material from disassembled lithium batteries) is mixed with the solution at 10% wt.
- the sample is sonicated at a high frequency (between 20 to 80 kHz) to remove the PVDF binder.
- the metal oxide powder is leached and separated by solvent extraction.
- the binders used in lithium-ion batteries are organic compounds that connect different parts of the batteries. These organics are very strong, adhesive and hydrophilic. The stable properties are essential to maintain the batteries' functions during charging and discharging cycles. The strength of binders becomes a problem in the recycling of Lithium-ion batteries.
- the current removal technology is based on either a thermal process (burning in a furnace at high temperature) or solvent extraction with expensive and hazardous solvents (such as NMP).
- the present surfactants avoid air pollution and hazardous solvents and reduce energy consumption. The process produced “black mass” without complex metal oxides (from the burning process) and enhanced the recovery of valuable metals.
- the 1:2:0.5 molar ratio of reactants (dodecyl phosphate, N(CH 3 )4OH, and Br(CH 2 ) 6 Br, respectively) and 3 h duration resulted to give maximum yield of anionic gemini surfactants.
- the structure of synthesized surfactant was investigated by modern analytical techniques, viz. FT-IR, 1 H NMR, 13 C NMR. Amphipathic disodium phosphates were obtained by neutralization of free acids with sodium hydroxide and their surface-active properties in aqueous solution were measured. These disodium phosphates possessed 77.3% anionic content and showed good water solubility.
- the present gemini surfactant(s) are made by reacting alkyl biphosphonate with the corresponding alcohol. The reaction occurs in tetrahydrofuran (THF) at room temperature.
- THF tetrahydrofuran
- the synthesized surfactants have been characterized by 1 H NMR and 13 C NMR.
- gemini surfactant for use in recycling lithium batteries is not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The gemini surfactant for use in recycling lithium batteries is an anionic surfactant having the generic formula CxH2x+1(CyH2y+1) PO4CzH2zPO4CxH2x+1(CyH2y+1). An example of the surfactant is shown as compound 1 below where (x=5, y=2, z=4). Current solvents used to remove polymer binders include Nmethyl-2-pyrrolidone (NMP), N—N-dimethylformamide (DMF), N—N-dimethylacetamide (DMAC), N—N-dimethylsulfoxide (DMSA), and ethanol. The benchmark solvent often used to dissolve polymer binders is NMP. However, the present surfactants are phosphate-based surfactants and are used with a phosphate-based solvent, namely, triethyl phosphate (TEP), which is cheaper and more environmentally friendly than NMP. However, TEP has weaker binder solubility than NMP. Thus, the present surfactants are used with sonication to remove polymer binders.
Description
The disclosure of the present patent application relates to surfactants, and particularly to a gemini surfactant for use in recycling lithium batteries.
In recent years, rechargeable lithium-ion batteries have become very popular as a portable source of electrical power for many different types of appliances. There is also some speculation that lithium batteries may provide an alternative to fossil fuels for powering electric automobiles. In view of the still-growing popularity of lithium batteries and the scarcity and expense of the materials used to make the batteries, it would be desirable to provide an efficient, commercially attractive process for recycling lithium batteries under relatively mild conditions.
Lithium batteries are made from various materials, including lithium, cobalt, aluminum, copper, manganese, nickel, and graphite. Since the metal layers tend to become delaminated, an organic polymer, most frequently polyvinylidene fluoride (PVDF) is used to bind the materials together, as well as to facilitate the exchanges of electric charges between the electrodes. Commercially, mechanical processes are used to separate the copper and aluminum foils used at the electrodes from the remaining fine particles (often referred to in the art as a “black mass”), which undergo pyrolysis or hydrometallurgical processes to remove the binder, which adheres to the fine particles. However, such processes often release hydrogen fluoride (HF) or fluorocarbons, requiring expensive scrubbers to remove harmful admissions, or use harsh solvents under extreme conditions.
Recently, research has focused on alternative surfactants to remove the PVDF binder under milder conditions. One such class of surfactants is gemini surfactants, which include two long hydrophobic tails, each tail headed by a small hydrophilic head, the heads being joined by a short bridge. However, to date, no such surfactant has been found suitable for commercial use in recycling lithium batteries.
Thus, a gemini surfactant for use in recycling lithium batteries solving the aforementioned problems is desired.
The gemini surfactant for use in recycling lithium batteries is an anionic surfactant having the generic formula CxH2x+1(CyH2y+1) PO4CzH2zPO4CxH2x+1(CyH2y+1). An example of the surfactant is shown as compound 1 below where (x=5, y=2, z=4). Current solvents used to remove polymer binders include Nmethyl-2-pyrrolidone (NMP), N—N-dimethylformamide (DMF), N—N-dimethylacetamide (DMAC), N—N-dimethylsulfoxide (DMSA), and ethanol. The benchmark solvent often used to dissolve polymer binders is NMP. However, the present surfactants are phosphate-based surfactants and are used with a phosphate-based solvent, namely, triethyl phosphate (TEP), which is cheaper and more environmentally friendly than NMP. However, TEP has weaker binder solubility than NMP. Thus, the present surfactants are used with sonication to remove polymer binders.
The surfactant(s) are made by reacting alkyl biphosphonate with the corresponding alcohol. The reaction occurs in tetrahydrofuran (THF) at room temperature.
In use, the surfactants are dissolved in triethyl phosphate (TEP) at a concentration of 1% wt. “Black mass” material (from disassembled lithium batteries) is mixed with the solution at 10% wt. The sample is sonicated at a high frequency (between 20 to 80 kHz) to remove the PVDF binder. The metal oxide powder is leached and separated by solvent extraction.
These and other features of the present subject matter will become readily apparent upon further review of the following specification.
The gemini surfactant for use in recycling lithium batteries is an anionic surfactant having the generic formula CxH2x+1(CyH2y+1) PO4CzH2zPO4CxH2x+1(CyH2y+1). An example of the surfactant is shown as compound 1 below where (x=5, y=2, z=4). Current solvents used to remove polymer binders include Nmethyl-2-pyrrolidone (NMP), N—N-dimethylformamide (DMF), N—N-dimethylacetamide (DMAC), N—N-dimethylsulfoxide (DMSA), and ethanol. The benchmark solvent often used to dissolve polymer binders is NMP. However, the present surfactants are phosphate-based surfactants and are used with a phosphate-based solvent, namely, triethyl phosphate (TEP), which is cheaper and more environmentally friendly than NMP. However, TEP has weaker binder solubility than NMP. Thus, the present surfactants are used with sonication to remove polymer binders.
The surfactant(s) are made by reacting alkyl biphosphonate with the corresponding alcohol. The reaction occurs in tetrahydrofuran (THF) at room temperature.
In use, the surfactants are dissolved in triethyl phosphate (TEP) at a concentration of 1% wt. “Black mass” material (from disassembled lithium batteries) is mixed with the solution at 10% wt. The sample is sonicated at a high frequency (between 20 to 80 kHz) to remove the PVDF binder. The metal oxide powder is leached and separated by solvent extraction.
The binders used in lithium-ion batteries are organic compounds that connect different parts of the batteries. These organics are very strong, adhesive and hydrophilic. The stable properties are essential to maintain the batteries' functions during charging and discharging cycles. The strength of binders becomes a problem in the recycling of Lithium-ion batteries. The current removal technology is based on either a thermal process (burning in a furnace at high temperature) or solvent extraction with expensive and hazardous solvents (such as NMP). The present surfactants avoid air pollution and hazardous solvents and reduce energy consumption. The process produced “black mass” without complex metal oxides (from the burning process) and enhanced the recovery of valuable metals.
The journal article by Shukla et al. entitled “Anionic gemini surfactants: synthesis and surface active properties”, Surface Review and Letters, Vol. 14, No. 05, pp. 991-997 (2007) describes a similar process for synthesizing the surfactant(s). As described in Shukla, the compounds have two phosphate groups and two long chains (dodecyl) and were prepared by two-step reaction: (i) phosphorylation of dodecanol with pyrophosphoric acid, (ii) reaction of dodecyl phosphate with N(CH3)4OH and 1,6-dibromo hexane. The effect of reaction variables like time and molar ratio of reactants on yield has also been reported. The 1:2:0.5 molar ratio of reactants (dodecyl phosphate, N(CH3)4OH, and Br(CH2)6Br, respectively) and 3 h duration resulted to give maximum yield of anionic gemini surfactants. The structure of synthesized surfactant was investigated by modern analytical techniques, viz. FT-IR, 1H NMR, 13C NMR. Amphipathic disodium phosphates were obtained by neutralization of free acids with sodium hydroxide and their surface-active properties in aqueous solution were measured. These disodium phosphates possessed 77.3% anionic content and showed good water solubility.
However, as noted above, the present gemini surfactant(s) are made by reacting alkyl biphosphonate with the corresponding alcohol. The reaction occurs in tetrahydrofuran (THF) at room temperature. The synthesized surfactants have been characterized by 1H NMR and 13C NMR.
It is to be understood that the gemini surfactant for use in recycling lithium batteries is not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.
Claims (7)
1. A gemini surfactant for use in recycling lithium batteries, comprising a compound having the formula CxH2x+1(CyH2y+1) PO4CzH2zPO4CxH2x+1(CyH2y+1), wherein x=5, y=2, and z=4.
2. The gemini surfactant according to claim 1 , wherein the gemini surfactant has the formula:
3. The gemini surfactant according to claim 1 , wherein the phosphate (PO4) groups are ionic, whereby the gemini surfactant has anionic, hydrophilic heads.
4. The gemini surfactant according to claim 1 , wherein the compound is soluble in a phosphate-based solvent.
5. The gemini surfactant according to claim 1 , wherein the gemini surfactant is soluble in triethyl phosphate (TEP).
6. A method for recycling lithium-ion batteries, including the steps of:
disassembling at least one lithium-ion battery to leave fine, particulate material from the battery joined by a binder of polyvinylidene fluoride in a form known as a black mass;
dissolving an anionic gemini surfactant of formula CxH2x+1(CyH2y+1) PO4CzH2zPO4CxH2x+1(CyH2y+1) in triethyl phosphate solvent at a concentration of 1% wt, wherein x=5, y=2, and z=4;
mixing the black mass from the lithium-ion battery with the solution of the anionic gemini surfactant at 10% wt to form a mixture; and
sonicating the mixture at a frequency between 20 kHz and 80 kHz to remove the polyvinylidene fluoride binder from the mixture and leave a metal oxide powder.
7. The method for recycling lithium-ion batteries according to claim 6 , further including the steps of:
leaching the metal oxide powder; and
separating metal oxides from the leached metal oxide powder by solvent extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18/186,584 US11802244B1 (en) | 2023-03-20 | 2023-03-20 | Gemini surfactant for use in recycling lithium batteries |
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| Application Number | Priority Date | Filing Date | Title |
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| US18/186,584 US11802244B1 (en) | 2023-03-20 | 2023-03-20 | Gemini surfactant for use in recycling lithium batteries |
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| US11802244B1 true US11802244B1 (en) | 2023-10-31 |
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